Multicolor film and process of preparing it



July 10, 1934. w, KRlEGER 1,966,412

MULTICOLOR FILM AND PROCESS OF PRPRING 15T Filed Feb. 24, 1952 Sens/flied me/Into@ @Mgmt/l @awr/dw,

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p Patented July l0, 1934 PATENT OFFICE MULTICOLOR FILM AND PROCESS F PREPABIN G Wilhelm Krieger, Wiesbaden-Biebtlch, Germany, assignor to Kalle t Co. Aktiengesellschaft, Wiesbadcn-Biebrich, Germany, a corporation of Germany Application February 24, 1932, Serial No. 594,959 In Germany February 28, 1931 21 Claims.

I'he present invention relates to multi-color films and to a process of preparing them.

One object of the present invention is a process of preparing a light-sensitive lm for the prol duction of two-color pictures or multi-color pictures. This process comprises the use of a iiim of a transparent material such as, for instance, a lm of regenerated cellulose or of a cellulose ester or ether. Said iilm is sensitized in the mass by the addition of light-sensitive substances and coated on one or both sides with light-sensitive layers, whereby it may be suitable to provide an inactinic intermediate layer between the'sensitized lm serving as support and the lightsensitive layers brought upon the said lm. In order to sensitize the said iilms in the mass, there are added to the mass serving for the preparation of the film such light-sensitive substances as permit of the production of a picture within the support. For this purpose stable diazo compounds such as are decomposed by the action of light may be employed, together, if desired, with azo components, as also bleaching-out dyestuffs, light-sensitive leuco compounds of basic dyes or vat dyestuifs and the like. These films can be prepared advantageously, for instance, according to the process disclosed in German speciiication No. 533,913, dated December 2l, 1927, in the name of Kalle & Co. A. G. and German specification No. 230,558. dater June 13, 1909, in the name of E. Brandenberger.

The light-sensitive external layers can be brought uponv the said lm in the usual manner, for instance, by coating the iilm with silver halide emulsions or bichromate colloidal emulsions, as alkali bichromate-gelatin or the like. Furthermore, it is possible to apply light-sensitive layers which contain stable diazo compounds as lightsensitive substances'either alone or in mixture with azo components, whereby all the other additions usual in diazo-type process, as for instance metal salts, thio-urea, organic acids and the like may be added. For the preparation of the inactinic intermediate layer which is applied on the film in the usual manner there may be used, for instance, a gelatin emulsion containing an inactinic colored dyestuii", for instance a yellow dyestui being water-soluble or soluble in the developing or fixing baths, or such dyestuiis as are decolorized by means of gaseous ammonia as, for instance, dior tri-phenylmethane dyestuis.

Another object of the present invention is the process of preparing multi-color iilms or pictures by means of the light-sensitive films described above. For that purpose there are prepared from (Cl. {l5-2) a pattern in the usual manner three uncolored negative parts pictures corresponding to the red, yellow and blue rays of light. These negatives or the corresponding uncolored positives prepared therefrom are used as patterns for the copying process. They are copied upon the transparent film sensitized in the mass and being coated on one or both sides with a light-sensitive layer, care being taken that each part picture is copied upon that light-sensitive layer which yields a dyestui picture corresponding to the kind oi the part picture. A negative part picture is used for copying when the corresponding sensitive layer is such as yielding a positive from a negative and a positive part picture, when the corresponding light-sensitive layer is such as to yield a positive from a positive.

In the following is described how the new process may advantageously be carried out.

By coating, for instance, a film, prepared by moulding a cellulose ester solution sensitized by the addition of diazo compounds together with azo components on both sides with a silver halide emulsion, the latter can be exposed to light under negative part pictures in the same manner as if the iilm serving as layer support were not sensitized. This on account of the slight sensitiveness of the diazo compounds being in the support'. The light-sensitive substance present in the layer support is in this case preferably exposed to light after the coloration of the external silver part pictures. If, with the said iilm, a sodium bichromate-gelatin emulsion is employed instead of a silver halide emulsion, it may be preferable to apply between the emulsion and the layer supportan inactinic intermediate layer, which disappears on watering after the bichromate layer has been exposed to light under a positive part picture. After such a iilm has been dried, the light-sensitive diazo compound present in the layer support is exposed to light and then developed in the usual manner. When using lightsensitive diazo -compounds for the preparation of the external layers it may also be preferable to apply between them and the layer support inactinic intermediate layers which, for instance,

' either disappear by the action of ammonia, or

anaslypha 11o light.

The accompanying drawing illustrates the invention.

Figs. 1-3 are similar schematic views showing the steps in the production of a picture in accordance with the process as described in Example 4.

Fig. 4 is a perspective view, partially in section, of a film made in accordance with the invention.

Fig. 1 shows the yellow picture produced by exposing a sensitized and coated film to light under a pattern and developing with gaseous ammonia. Upon one side of the film thus obtained, the blue portion of the picture is produced by an imbibition process, thus yielding the picture shown in Fig. 2 containing the yellow and the blue parts. Then the red portion of the picture is produced upon the other side of the film and the result is the picture shown in Fig. 3 containing the complete reproduction in three colors.

The film shown'in Fig. 4 consists of a layer 2 of.' transparent cellulosic material sensitized in the mass which carries on one side a sensitized colloidal layer 1 and on the other side a sensitized colloidal layer 3.

The following examples illustrate the invention.

l. A cellulose ester film which is sensitized in the mass by the addition of the diazo borofiuoride of para-aminomonoethyl ortho toluidine and phenol, is coated on each side with a silver halide emulsion. After the external part pictures have been formed by exposing the external layers to light each under the corresponding negative part picture and subsequently developing in the usual manner, they are bleached according to known methods; the picture on one side is dyed blue and that on the other side is dyed red according to the uvachrome method (mordant dye processes). After the film has been dried, the third part picture is formed by exposing the internal lightsensitive film under a corresponding positive part picture through the blue part picture and subsequent development by means of gaseous ammonia, it being preferable to insert a blue filter. The loss of light which occurs is relatively small, since the diazo layers generally are only sensitive to blue It may be advantageous to arrange between the silver halide emulsions and the layer support an inactinic intermediate layer which, on exposure of the silver halide emulsions, prevents the light from reaching the wrong side.

2. A cellulose ether film is sensitized in the mass by the diazo compound of the 1.2.4-aminonaphtholsulfonic acid and resorcin. This film is coated on both sides with a sodium bichromategelatin emulsion. The two external bichromate Alayers are exposed to iight under a positive part picture, watered and dried. Then the internal sensitized film is exposed to light under the positive part picture corresponding to the red rays of light and may be immediately developed by means of ammonia. The film is then again watered and the two.external part pictures are dyed in the usual manner, so that one picture is dyed yellow and the other is dyed blue, whereas the internal sensitized film has yielded a red picture. It is also possible firstly to dye the two external bichromate layers yellow and blue directly after they have been exposed to light and only then to expose the layer support through the blue picture, as indicated in Example 1, and develop it by means of ammonia. In this case it is also preferable to use an inactinic, intermediate layer which disappears on watering.

3. A cellulose ester solution is mixed with resorcin and the diazo compound from paraaminomonoethyl-ortho-toluidine and a film is prepared in the usual manner by moulding this solution. The film thus produced is coated on one side with a gelatin emulsion containing 1.8.2.4-aminonaphtholdisulfonic acid and the diazo compound from para-aminomonoethylortho-toluidine. After the exposure to light under corresponding positive part pictures and subsequent development with gaseous ammonia a blue picture is obtained in the external layer and an orange picture in the layer support. It may be advantageous to arrange between the layer support and the gelatine emulsion an inactinic intermediate layer, for instance a layer containing a dior tri-phenylmethane dyestuff which'rdisappears on developing with ammonia.

4. A cellulose ester film which is sensitized in the mass as indicated in Example 1, is coated on both sides with a pure gelatin layer. After exposure to light under a. positive part picture and development with gaseous ammonia, the yellow part picture is produced in the layer support, whilst the red part picture and the blue part picture are produced on the film by the imbibition process.

5. Alm made from regenerated cellulosewhlch is sensitized in the mass by means of a bleaching-out dyestuff, for instance fiavinduline, and the external surface of which is lacquered by means of a cellulose ester lacquer is coated on one side with a Prussian blue gelatin preparation and on the other side with a bichromate-gelatin emulsion. After the external layers have been exposed to light under corresponding part pictures and developed in the usual manner, a red picture is produced on one side and a blue picture is produced on the other side in known manner. The sensitized layer support is then exposed to light under a positive part picture through the blue part picture whereby a yellow bleaching-out picture is obtained.

I claim:

1. The process of preparing multi-color films which comprises producing one colored part picture in the mass of a transparent film of a cellulose material and the other colored part pictures upon the surfaces of the film.

2, The process of preparing multi-color films which comprises producing one colored part picture in the mass of a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers and the other colored part pictures upon the surfaces of the film.

3. The process of preparing multi-color films which comprises sensitizing a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive substances, coating the surfaces of this film with light-sensitive layers, exposing the said layers to light kunder a pattern, then causing light to act upon the sensitized internal film through a pattern and one of the external layers for producing the internal part picture and developing the pictures thus obtained.

4. The process of preparing multi-color films which comprises sensitizing a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive substances, covering that film on its surfaces with an inactinic gelatin layer, then coating the external surfaces of this film with light-sensitive layers, exposing the external layers to light under a pattern, removing the inactinic intermediate layer, then causing light t0 act upon the sensitized internal film through a pattern and one of the external layers for producing the internal part picture and developing the pictures thus obtained.

5. The process of preparing multi-color films which comprises impregnating a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive substances, coating the surfaces of this film with gelatin layers, exposing the film thus obtained to light under a pattern, developing the picture formed by this process in the internal film and producing colored part pictures upon the external surfaces of the gelatin layers by means of the imbibition process.

6. The process of preparing multi-color films which comprises sensitizing a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive substances, coating the external surfaces of this film with light-sensitive layers, exposing the external layers to light under a pattern, developing and coloring the pictures thus obtained, then causing light to act upon the sensitized internal film through a pattern and the external blue part picture for producing the internal part picture and developing the pictures thus obtained.

7. The process of preparing multi-color films which comprises sensitizing a transparent nlm of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethersl in its mass with light-sensitive substances, covering that fllm on its surfaces with an inactinic layer, then coating the external surfaces of this film with light-sensitive layers, exposing the external layers to light under a pattern, developing and coloring the pictures thus obtained, removing the inactinic intermediate layer, causing light to act upon the sensitized internal film through a pattern and the external blue part picture for'producing the internal part picture and developing the picture thus obtained.

8. The process of preparing multi-color films which comprises sensitizing a transparent lm of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive stable diazo compounds in mixture with azo components, coating the external surfaces of this film with light sensitive layers, the light-sensitiveness of which depends upon the presence of silver halide, exposing the external layers to light under a pattern, developing and coloring the part pictures thus obtained. then exposing the sensitized internal film through a pattern and the external blue part picture and developing the picture in the internal nlm by means of gaseous ammonia.

9. The process of preparing multi-color lms which comprises sensitizing a transparent film of a material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers in its mass with light-sensitive stable diazo compounds in mixture with azo components, cover- 10. The process of preparing multi-color films which comprises impregnating a transparent film of a material of the group consisting of regenerunder a pattern, developing the picture formed by this process in the internal film by means of gaseous ammonia and producing colored part pictures upon the external surfaces of the gelatin layers by means of the imbibition process.

11. As new products, multi-color films of a transparent cellulosic material being sensitized in the mass and coated with colloidal layers.

12. As new products, multi-color films of a transparent. cellulose material being sensitized in the mass and coated with sensitized colloidal layers.

13. As new products, multi-'color films of a transparent material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass and coated with colloidal layers.

14. As new products, multi-color films of a transparent material of 'the group consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass and coated with sensitized colloidal layers. l

15. As new products, multi-color films of a transparent material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass by stable, light-sensitive diazo compounds, and coated with colloidal layers.

16. As new products, multi-color films of a transparent material of thegroup consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass by stable, light-sensitive diazo compounds, and coated with colloidal layers being sensitized by silver halides.

17. As new products, multi-color films of a transparent material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass by means of a stable diazo compound in mixture with an azo component and coated with gelatin layers.

18. As`new products, multi-color films of a transparent material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers being sensitized in the mass by means of a stable diazo compound in mixture with an azo component and coated with gelatin layers being sensitized by silver halides.

19. As new products, multi-color films of a transparent cellulosic material containing one colored part picture in the mass of the transparent film and the other colored part pictures directly on the surfaces of said film.

20. As new products, multi-color filmsy of a transparent material of the group consisting of regenerated cellulose, cellulose esters and cellulose ethers containing one colored part picture in the mass of the transparent film and the other colored part pictures. in colloidal layers applied directly on the surfaces of said film.

21. As new products, multi-color films of a transparent material of the group consisting oi' regenerated cellulose, cellulose esters and cellulose ethers containing one colored part picture in the mass of the transparent film and the other colored part pictures in gelatin layers applied directly on the surfaces of said film.

` WILHELM KRIEGER. 

